Full text of DOI:10.1002/ejoc.201800778

DOI: 10.1002/ejoc.201800778
Full Paper
Sulfonylation with Thiosulfonates
Complementary Strategy for Regioselective Synthesis of Diverse
ꢀ-Hydroxysulfones from Thiosulfonates
Soobin Son,[a] Pranab K. Shyam,[a] Hyowon Park,[a] Ilgyo Jeong,[a] and Hye-Young Jang*[a]
Abstract: The regioselective synthesis of variously substituted tion mechanism to nucleophilic addition involving sulfinate an-
ꢀ-hydroxysulfones from thiosulfonates was developed. The re- ions to afford 1° and 2° ꢀ-hydroxysulfones. By using both proto-
actions of thiosulfonates and alkenes via a peroxy radical inter- cols, the regiochemical outcome of the ꢀ-hydroxysulfones syn-
mediate provided 2° and 3° ꢀ-hydroxysulfones in good yields. thesized from thiosulfonates was diversified.
The presence of epoxides instead of alkenes changed the reac-
Introduction
The ꢀ-hydroxysulfone motif is widely prevalent in biologically
active compounds, including pharmaceutical drug candi-
dates.[1] Therefore, tremendous efforts have been devoted to
the development of protocols for the efficient and selective syn-
thesis of ꢀ-hydroxysulfones:[2] reduction of ketosulfones;[3] pho-
tocatalytic,[4] transition-metal-catalyzed,[5] and oxidant-medi-
ated hydroxy sulfonylation of alkenes;[6] and reaction of epox-
ides with sulfinate salts.[7] In particular, direct coupling of the
sulfonyl group with hydrocarbon scaffolds is considered a sim-
ple and convenient protocol to produce ꢀ-hydroxysulfones.
Sulfinates (sulfinic acids) as sulfonyl group precursors are often
employed to form ꢀ-hydroxysulfones, where sulfonyl groups are
added to the less substituted position of alkenes or epoxides
(Scheme 1).[6,7] Considering the structural diversity of ꢀ-
Scheme 1. Synthesis of ꢀ-hydroxysulfones.
hydroxysulfones in synthetically and biologically important
building blocks, the reaction conditions for obtaining diverse
with alkenes and aliphatic epoxides afforded 2° and 3° ꢀ-
hydroxysulfones with regioselectivity control must be investi-
hydroxysulfones, while the reactions of thiosulfonates and aro-
gated.
matic epoxides provided 1° ꢀ-hydroxysulfones with complete
Our research group has been interested in sulfonylation us-
regioselectivity (Scheme 1). Detailed synthetic conditions with
ing thiosulfonates, since we identified catalytic methods for the
related studies to support the proposed mechanisms are pre-
formation of thiosulfonates from thiols.[8] Accordingly, we inves-
sented.
tigated the utility of thiosulfonates as sulfonyl group transfer-
ring agents under non-radical and radical conditions. Nucleo-
philic addition of the sulfonyl anion (sulfinate anion) generated
from thiosulfonates with various electrophiles was conducted
Results and Discussion
The coupling reaction of S-phenyl benzenesulfonothiolate 1a
with styrene 1b was investigated under the conditions listed in
Table 1. The reaction of 1a and 1b in the presence of KI in
CH3CN gave vinyl sulfone 1d exclusively in 92 % yield (entry
1).[9b,10] Changing the solvent from CH3CN to ethyl acetate
(EtOAc) provided 2° ꢀ-hydroxysulfones 1c (28 % yield) and 1d
(27 % yield) (entry 2). The addition of H2O increased the yield
of 1c up to 70 % while suppressing the formation of 1d to 15 %
(entry 3). Along with H2O, triethylamine (TEA) was added to
increase the yield of 1c to 75 % and decrease the yield of 1d
to 3 % (entry 4). It is not clear, but the effect of solvent and the
presence of base and water are combined to increase the yield
to furnish a wide range of sulfones and sulfonamides. Radical
coupling reactions of thiosulfonates were conducted to afford
vinyl sulfones.[9] As a continuing effort toward utilizing thiosulf-
onates as useful synthetic building blocks, we propose a com-
plementary strategy to form differently substituted ꢀ-hydroxy-
sulfones using thiosulfonates. The reactions of thiosulfonates
[a] Department of Energy Systems Research, Ajou University,
Suwon, Korea
E-mail: hyjang2@ajou.ac.kr
http://ajou.ac.kr/~hyjang2
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201800778.
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of ꢀ-hydroxysulfones while suppressing vinyl sulfone formation. fully to afford 8c–10c. Next, α- and ꢀ-methyl-substituted
The absence of oxygen diminished the formation of 1c (entry styrenes were subjected to the reaction conditions. The reaction
5). When NaI and NH4I were used, the yield of 1c was slightly of α-methyl styrene with phenylthiosulfonate afforded 11c in
reduced (entries 6 and 7).
75 % yield, and ꢀ-methyl styrene reacted with phenylthiosulfo-
nate to form 12c in 71 % yield under slightly modified condi-
tions.[11] Electron-deficient alkenes such as methyl methacrylate
and benzyl methacrylate were examined in the present reac-
tion, and 13c and 14c were obtained in 65 % yields. To compare
the reactivity of alkenes, allyl-substituted methacrylate was al-
lowed to react with 1a, which resulted in selective sulfonyl ad-
dition to conjugated alkenes to provide 3° ꢀ-hydroxysulfone
15c in 60 % yield.
Table 1. Optimizing the reaction of 1a with 1b.[a]
Coupling reactions of 1a with styrene oxide 1b′ were con-
ducted under the conditions in Table 2. A mixture of 1a, 1b′,
and KI was stirred in EtOAc/H2O at 80 °C to afford 2° ꢀ-hydroxy-
sulfones 1c in 7 % yield and 1° ꢀ-hydroxysulfones 1e in 35 %
yield (entry 1). Oxygen had no influence on the reactions; thus,
the reactions were carried out under nitrogen atmosphere.
Upon the addition of TEA, the yield of 1e increased to 49 %,
while the yield of 1c remained as low as 2 % (entry 2). To exam-
ine the effect of salts, NaI and NH4I were added to the reaction
mixture, and the best result was observed for NaI (entries 2–4).
Upon changing the base from TEA to pyridine, the yield of 1e
was dramatically increased to 86 % (entry 5).
[a] Reaction conditions: 1a (0.25 mmol), 1b (0.5 mmol), EtOAc/H2O (9:1 vol-
ume ratio); [b] under N2.
The conditions from Table 1 were employed for the reactions
of various thiosulfonates and alkenes, as shown in Figure 1. The
reactions of substituted thiosulfonates with styrene afforded
the desired 2° ꢀ-hydroxysulfones in good yields (2c–4c). The
coupling of phenylthiosulfonate and substituted styrenes also
provided 2° ꢀ-hydroxysulfones in good yields (5c–7c). Substi-
tuted thiosulfonates and substituted styrenes reacted success-
Table 2. Optimizing the reaction of 1a with styrene epoxide 1b′.[a]
[a] Reaction conditions: 1a (0.25 mmol), 1b (0.5 mmol), EtOAc/H2O (9:1 vol-
ume ratio).
The reactions of various thiosulfonates and epoxides were
conducted (Figure 2). Substituted thiosulfonates reacted with
styrene oxide to give 1° ꢀ-hydroxysulfones in good yields (2e–
5e). Substituted styrene oxides also participated in the reaction
to form 1° ꢀ-hydroxysulfones 6e and 7e. An aliphatic epoxide,
1,2-epoxyhexane, was converted to 2° ꢀ-hydroxysulfone 8e in
78 % yield. The reaction of 2-phenoxyoxirane also favored the
formation of 2° ꢀ-hydroxysulfone 9e in 71 % yield.
Although the reactions of alkenes and epoxides are carried
out under similar conditions with the use of KI, an organic base,
and aqueous EtOAc, it is difficult to conclude if they proceed via
the same mechanism. To probe the mechanism, the following
control experiments were performed (Scheme 2 and Scheme 3).
In the case of reactions using thiosulfonates and alkenes, an
oxygen atom derived from oxygen gas is incorporated during
the coupling step.[6a] Since our reaction is conducted under
oxygen, we assumed that the oxygen atom is derived from the
Figure 1. Substrate scope for coupling of thiosulfonates and alkenes.
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Figure 2. Substrate scope of reactions of thiosulfonates and epoxides.
Scheme 3. Control experiments for coupling of thiosulfonates and epoxide.
Control experiments for the reaction of thiosulfonates and
epoxides were conducted, as listed in Scheme 3. NaI was re-
placed with NaBr and NaPF6 [Equation (1)] to demonstrate that
the presence of iodides is essential to this reaction. The reaction
of PhSO2I 1a′ with styrene oxide did not provide any hydroxy-
sulfone under the conditions without NaI [Equation (2)]. The
presence of TEMPO did not completely prevent the reaction,
indicating that this reaction may not follow the radical pathway
[Equation (3)]. Finally, the reaction of PhSO2Na gave 1e in lower
yield [Equation (4)]. Analogous to alkenes, thiosulfonates gave
more products than PhSO2Na under our reaction conditions.
Based on the control experiments (Scheme 2 and Scheme 3),
a radical mechanism for the reaction of thiosulfonates and alk-
enes, and a nucleophilic mechanism for the reaction of thiosulf-
onates and epoxides are proposed in Scheme 4. In the radical
mechanism, thiosulfonates react with iodide to afford PhSO2I,
which is dissociated into sulfonyl radicals and iodide radi-
cals.[9b,9c] Upon the introduction of styrene, intermediate II is
Scheme 2. Control experiments for coupling of thiosulfonates and alkenes.
oxygen gas. However, the reaction proceeded even in the ab- formed. Oxygen reacts with II to form peroxy radical species,
sence of oxygen, albeit with low product yield (Table 1, entry which are trapped by another molecule of II. Subsequent ho-
5), and the addition of water promoted the formation of molytic cleavage of the peroxy linkage provides intermediate
hydroxysulfone products. In an experiment carried out in the III.[6d,12] With assistance of water and PhS–, ꢀ-hydroxysulfones
presence of 18O-labeled H2O, 18O-labeled products were ob- are formed. As a minor pathway, intermediate II undergoes
served as the minor product, implying that small amounts of oxidation to form carbocationic IV, and the addition of water
oxygen might be delivered from H2O (Scheme 2, equation 1). to the carbocation provides the same product. This route may
The reaction of PhSO2I 1a′ indicated that PhSO2I generated support the result of the 18O-labelling experiment [Scheme 2,
from PhSO2SPh and KI is a key intermediate (equation 2). The Equation (1)]. To account for the control experimental results of
addition of TEMPO completely inhibited the formation of 1c, epoxide reactions, the nucleophilic addition of sulfinate anions
implying that this reaction may proceed through a radical is proposed. In this reaction, amine bases are added to the sulf-
mechanism (equation 3). To compare the reactivity of thiosulf- enyl group to form intermediate V. Upon the addition of iod-
onates, PhSO2Na, a well-known sulfonyl precursor, was sub- ides, reactive sodium sulfinates are generated to react with ep-
jected to the reaction conditions and 1c was formed in dimin- oxide, resulting in ꢀ-hydroxysulfones. The coordination of the
ished yield (equation 4).
sodium cation may build up cationic character proximal to the
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Scheme 4. Plausible reaction mechanisms.
1-Phenyl-2-(phenylsulfonyl)ethan-1-ol (1c): The representative
experimental procedure was applied to S-phenyl benzenesulfono-
thioate (62.6 mg, 0.25 mmol) with styrene (52.1 mg, 0.50 mmol) to
phenyl group of the epoxides, thus inducing the observed
regiochemistry.[7d] Thiosulfonates in the presence of iodides
and amine bases lead to the formation of PhSO2I for the radical
pathway or a sulfinate anion for the nucleophilic pathway, de-
pending on the reaction partners.
1
afford 1c as white solid in 75 % (49.2 mg) yield. M.p.: 91–93 °C. H
NMR (CDCl3, 600 MHz): δ = 7.96 (d, J = 6.9 Hz, 2 H), 7.69 (t, J =
7.6 Hz, 1 H), 7.59 (t, J = 7.9 Hz, 2 H), 7.26–7.33 (m, 5 H), 5.28 (d, J =
10.3 Hz, 1 H), 3.67 (d, J = 2.1 Hz, 1 H), 3.50 (dd, J = 14.5, 9.6 Hz, 1
H), 3.34 (dd, J = 14.5, 2.1 Hz, 1 H) ppm. 13C NMR (CDCl3, 150 MHz):
δ = 140.8, 139.4, 134.2, 129.6, 128.9, 128.5, 128.1, 125.8, 68.6, 64.1
ppm. HRMS (EI, m/z): calcd. for C14H14O3S [M]+, 262.0664; found
Conclusions
In this study, we investigated the reactivity of thiosulfonates to
form ꢀ-hydroxysulfones in the presence of KI, an organic base,
and an aqueous solvent. Depending on the reaction compo-
nent (alkenes or epoxides), sulfonyl groups are delivered to the
more substituted or less substituted site of the product to form
various 1° to 3° ꢀ-hydroxysulfones in good yields. By conduct-
ing control experiments, we proposed a radical mechanism for
the coupling of thiosulfonates and alkenes, and a nucleophilic
addition mechanism for the reaction of thiosulfonates and ep-
oxides.
262.0665. FTIR (neat): ν = 3478, 2903, 1603, 1447, 1282, 1134,
˜
1061 cm–1
.
2-[(4-Fluorophenyl)sulfonyl]-1-phenylethan-1-ol (2c): The repre-
sentative experimental procedure was applied to S-(4-fluorophenyl)
4-fluorobenzenesulfonothioate (71.6 mg, 0.25 mmol) with styrene
(58 μL, 0.50 mmol) to afford 2c as white solid in 79 % yield. M.p.:
104–105 °C. 1H NMR (CDCl3, 600 MHz): δ = 7.96–7.98 (m, 2 H), 7.24–
7.34 (m, 7 H), 5.29 (d, J = 10.3 Hz, 1 H), 3.52 (dd, J = 14.5, 9.6 Hz, 2
H), 3.34 (dd, J = 14.5, 2.1 Hz, 1 H) ppm. 13C NMR (CDCl3, 150 MHz):
δ = 166.1 (d, J = 255.6 Hz), 140.7, 135.5 (d, J = 3.0 Hz), 131.1 (d, J =
10.1 Hz), 129.0, 128.6, 125.8, 116.9 (d, J = 21.6 Hz), 68.7, 64.2 ppm.
HRMS (EI, m/z): calcd. for C14H13FO3S [M]+, 280.0569; found
280.0572. FTIR (neat): ν = 3478, 2927, 1590, 1493, 1281, 1132,
Experimental Section
˜
1057 cm–1
.
General Procedure for the Synthesis of ꢀ-Hydroxysulfones with
Alkenes: Styrene (52.1 mg, 0.50 mmol) was added to a mixture
of S-phenyl benzenesulfonothiolate (62.6 mg, 0.25 mmol) and KI
(83.0 mg, 0.50 mmol) with 0.90 mL of ethyl acetate and 0.10 mL of
H2O in a 5 mL round-bottom flask under O2 atmosphere. The reac-
tion was stirred at 80 °C for 16 h. Then, it was cooled, dried with
sodium sulfate, concentrated through a rotary evaporator, and puri-
fied by column chromatography on a silica gel column eluting with
10 % ethyl acetate in hexane to afford the desired product.
2-[(4-Chlorophenyl)sulfonyl]-1-phenylethan-1-ol (3c): The repre-
sentative experimental procedure was applied to S-(4-chlorophenyl)
4-chlorobenzenesulfonothioate (79.8 mg, 0.25 mmol) with styrene
(58 μL, 0.50 mmol) to afford 3c as white solid in 74 % yield. M.p.:
105–106 °C. 1H NMR (CDCl3, 600 MHz): δ = 7.88 (dd, J = 6.9, 2.1 Hz,
2 H), 7.55 (dd, J = 6.9, 2.1 Hz, 2 H), 7.26–7.33 (m, 5 H), 5.28 (d, J =
9.6 Hz, 1 H), 3.52 (dd, J = 14.5, 9.6 Hz, 1 H), 3.45 (d, J = 2.8 Hz, 1 H),
3.34 (dd, J = 14.5, 2.1 Hz, 1 H) ppm. 13C NMR (CDCl3, 150 MHz): δ =
141.0, 140.7, 137.9, 129.9, 129.7, 129.0, 128.6, 125.8, 68.7, 64.2 ppm.
HRMS (EI, m/z): calcd. for C14H13ClO3S [M]+, 296.0274; found
General Procedure for the Synthesis of ꢀ-Hydroxysulfones with
Epoxides: Styrene oxide (60.1 mg, 0.50 mmol) was added to a mix-
ture of S-phenyl benzenesulfonothiolate (62.6 mg, 0.25 mmol) and
NaI (75.0 mg, 0.50 mmol) with 0.90 mL of ethyl acetate and 0.10 mL
of H2O in a 5 mL round-bottom flask under N2 atmosphere. The
reaction was stirred at 80 °C for 16 h. Then, it was cooled, dried
with sodium sulfate, concentrated through a rotary evaporator, and
purified by column chromatography on a silica gel column eluting
with 15 % ethyl acetate in hexane to afford the desired product.
296.0276. FTIR (neat): ν = 3457, 2934, 1580, 1474, 1301, 1134,
˜
1060 cm–1
.
1-Phenyl-2-tosylethan-1-ol (4c): The representative experimental
procedure was applied to S-(p-tolyl) 4-methylbenzenesulfonothio-
ate (69.6 mg, 0.25 mmol) with styrene (52 mg, 0.50 mmol) to afford
4c as colorless oil in 75 % (52.0 mg) yield. 1H NMR (CDCl3, 600 MHz):
δ = 7.84–7.85 (m, 2 H), 7.39 (d, J = 7.6 Hz, 2 H), 7.26–7.34 (m, 5 H),
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5.25–5.26 (m, 1 H), 3.76–3.66 (1 H), 3.47 (dd, J = 14.5, 10.3 Hz, 1 H),
94–96 °C. 1H NMR (CDCl3, 600 MHz): δ = 7.82 (d, J = 8.3 Hz, 2 H),
3.32 (dd, J = 14.5, 2.1 Hz, 1 H), 2.47 (s, 3 H) ppm. 13C NMR (CDCl3, 7.39 (d, J = 8.3 Hz, 2 H), 7.28–7.29 (m, 2 H), 7.23 (d, J = 8.3 Hz, 2 H),
150 MHz): δ = 145.4, 140.8, 136.3, 130.2, 128.9, 128.4, 128.1, 125.8,
5.24 (d, J = 10.3 Hz, 1 H), 3.80 (d, J = 2.1 Hz, 1 H), 3.42 (dd, J = 14.5,
10.3 Hz, 1 H), 3.28 (dd, J = 14.5, 1.4 Hz, 1 H), 2.47 (s, 3 H) ppm. 13C
NMR (CDCl3, 150 MHz): δ = 145.5, 139.3, 136.1, 134.2, 130.3, 129.0,
128.1, 127.2, 68.0, 64.0, 21.8 ppm. HRMS (EI, m/z): calcd. for
68.6, 64.1, 21.8 ppm. HRMS (EI, m/z): calcd. for C15H16O3S [M]+,
276.0820; found 276.0817. FTIR (neat): ν = 3501, 3061, 1597, 1494,
˜
1300, 1135, 1086 cm–1
.
C15H15ClO3S [M]+, 310.0430; found 310.0432. FTIR (neat): ν = 3482,
˜
1-(4-Fluorophenyl)-2-(phenylsulfonyl)ethan-1-ol (5c): The repre-
sentative experimental procedure was applied to S-phenyl
2919, 1597, 1488, 1283, 1135, 1085 cm–1
.
benzenesulfonothiolate (62.6 mg, 0.25 mmol) with 4-fluorostyrene 2-[(4-Chlorophenyl)sulfonyl]-1-(p-tolyl)ethan-1-ol (10c): The rep-
(61 mg, 0.50 mmol) to afford 5c as yellow oil in 80 % (56.1 mg)
yield. H NMR (CDCl3, 600 MHz): δ = 7.96 (dd, J = 8.3, 1.4 Hz, 2 H),
resentative experimental procedure was applied to S-(4-chloro-
phenyl) 4-chlorobenzenesulfonothioate (79.8 mg, 0.25 mmol) with
4-methylstyrene (59.1 mg, 0.50 mmol) to afford 10c as white solid
1
7.69–7.71 (m, 1 H), 7.60 (t, J = 7.9 Hz, 2 H), 7.28 (dq, J = 9.0, 2.7 Hz,
2 H), 6.99–7.02 (m, 2 H), 5.28 (d, J = 9.0 Hz, 1 H), 3.73 (s, 1 H), 3.47
1
in 74 % (57.1 mg) yield. M.p.: 60–63 °C. H NMR (CDCl3, 600 MHz):
(dd, J = 14.5, 10.3 Hz, 1 H), 3.31 (dd, J = 14.5, 2.1 Hz, 1 H) ppm. 13C δ = 7.88 (d, J = 8.3 Hz, 2 H), 7.55 (d, J = 8.3 Hz, 2 H), 7.15 (dd, J =
NMR (CDCl3, 150 MHz): δ = 162.6 (d, J = 245.6 Hz), 139.2, 136.6 (d,
J = 2.9 Hz), 134.3, 129.6, 128.1, 127.6 (d, J = 8.6 Hz), 115.8 (d, J =
25.5, 8.3 Hz, 4 H), 5.24 (d, J = 9.6 Hz, 1 H), 3.52 (dd, J = 14.5, 10.3 Hz,
1 H), 3.32–3.34 (m, 2 H), 2.32 (s, 3 H) ppm. 13C NMR (CDCl3,
21.6 Hz), 68.0, 64.0 ppm. HRMS (EI, m/z): calcd. for C14H13FO3S [M]+, 150 MHz): δ = 141.0, 138.5, 138.0, 137.7, 129.9, 129.7, 129.6, 125.7,
280.0569; found 280.0567. FTIR (neat): ν = 3334, 2983, 1605, 1510,
68.6, 64.2, 21.3 ppm. HRMS (EI, m/z): calcd. for C15H15ClO3S [M]+,
˜
1264, 1137, 1086 cm–1
.
310.0430; found 310.0434. FTIR (neat): ν = 3516, 2920, 1577, 1476,
˜
1277, 1138, 1085 cm–1
.
1-(4-Chlorophenyl)-2-(phenylsulfonyl)ethan-1-ol (6c): The repre-
sentative experimental procedure was applied to S-phenyl
benzenesulfonothiolate (62.6 mg, 0.25 mmol) with 4-clorostyrene
2-Phenyl-1-(phenylsulfonyl)propan-2-ol (11c): The representative
experimental procedure was applied to S-phenyl benzenesulfono-
(69 mg, 0.50 mmol) to afford 6c as yellow solid in 75 % (55.6 mg) thioate (62.6 mg, 0.25 mmol) with α-methylstyrene (59.1 mg,
1
yield. M.p.: 102–103 °C. H NMR (CDCl3, 600 MHz): δ = 7.95 (dd, J =
8.3, 1.4 Hz, 2 H), 7.70 (t, J = 7.6 Hz, 1 H), 7.60 (t, J = 7.6 Hz, 2 H),
7.28–7.30 (m, 2 H), 7.24 (d, J = 8.3 Hz, 2 H), 5.27 (d, J = 10.3 Hz, 1
H), 3.74 (s, 1 H), 3.46 (dd, J = 14.5, 9.6 Hz, 1 H), 3.31 (dd, J = 14.5,
2.1 Hz, 1 H) ppm. 13C NMR (CDCl3, 150 MHz): δ = 139.2, 139.2, 134.4,
0.50 mmol) to afford 11c as white solid in 75 % (51.7 mg) yield.
M.p.: 104–106 °C. 1H NMR (CDCl3, 600 MHz): δ = 7.59 (d, J = 6.9 Hz,
2 H), 7.52 (t, J = 7.2 Hz, 1 H), 7.37 (t, J = 7.9 Hz, 2 H), 7.26–7.29 (m,
2 H), 7.14–7.19 (m, 3 H), 4.61 (s, 1 H), 3.74 (d, J = 14.5 Hz, 1 H), 3.62
(d, J = 14.5 Hz, 1 H), 1.71 (s, 3 H) ppm. 13C NMR (CDCl3, 150 MHz):
134.3, 129.7, 129.1, 128.1, 127.2, 68.0, 64.0 ppm. HRMS (EI, m/z): δ = 144.5, 140.4, 133.6, 129.2, 128.4, 127.6, 127.4, 124.8, 73.3, 66.8,
calcd. for C14H13ClO3S [M]+, 296.0274; found 296.0271. FTIR (neat): 30.9 ppm. HRMS (EI, m/z): calcd. for C15H16O3S [M]+, 276.0820; found
ν = 3483, 2924, 1582, 1486, 1283, 1139, 1082 cm–1
.
276.0816. FTIR (neat): ν = 3534, 2923, 1583, 1448, 1375, 1356, 1305,
˜
˜
1154 cm–1
.
2-(Phenylsulfonyl)-1-(p-tolyl)ethan-1-ol (7c): The representative
experimental procedure was applied to S-phenyl benzenesulfono-
cis-1-Phenyl-2-(phenylsulfonyl)propan-1-ol (12c): The represent-
thiolate (62.6 mg, 0.25 mmol) with 4-methylstyrene (59 mg, ative experimental procedure was applied to S-phenyl benzene-
0.50 mmol) to obtained 7c as yellow solid in 75 % (51.8 mg) yield.
M.p.: 59–60 °C. 1H NMR (CDCl3, 600 MHz): δ = 7.95 (dd, J = 8.3,
1.4 Hz, 1 H), 7.68 (t, J = 7.6 Hz, 1 H), 7.58 (t, J = 7.9 Hz, 1 H), 7.16
sulfonothioate (62.6 mg, 0.25 mmol) with trans-ꢀ-methylstyrene
(88.6 mg, 0.75 mmol) to afford 12c as white solid in 71 % (48.9 mg)
yield. M.p.: 82–83 °C. H NMR (CDCl3, 600 MHz): δ = 7.96–7.97 (m,
1
(d, J = 8.3 Hz, 1 H), 7.11 (d, J = 8.3 Hz, 1 H), 5.23 (d, J = 9.6 Hz, 1 2 H), 7.70 (t, J = 7.6 Hz, 1 H), 7.61 (t, J = 7.9 Hz, 2 H), 7.32 (t, J =
H), 3.58 (d, J = 2.1 Hz, 1 H), 3.49 (dd, J = 14.5, 9.6 Hz, 1 H), 3.32 (dd,
J = 14.5, 2.1 Hz, 1 H), 2.30 (s, 2 H) ppm. 13C NMR (CDCl3, 150 MHz):
δ = 139.4, 138.3, 137.8, 134.2, 129.6, 129.6, 128.1, 125.7, 68.5, 64.1,
21.2 ppm. HRMS (EI, m/z): calcd. for C15H16O3S [M]+, 276.0820; found
7.6 Hz, 2 H), 7.24–7.26 (m, 3 H), 5.52 (s, 1 H), 3.29 (s, 1 H), 3.20–3.24
(m, 1 H), 1.19 (d, J = 6.9 Hz, 3 H) ppm. 13C NMR (CDCl3, 150 MHz):
δ = 140.0, 137.5, 134.2, 129.5, 128.9, 128.6, 127.9, 125.7, 69.4, 65.8,
5.9 ppm. HRMS (EI, m/z): calcd. for C15H16O3S [M]+, 276.0820; found
276.0822. FTIR (neat): ν = 3488, 2924, 1584, 1513, 1281, 1132,
276.0818. FTIR (neat): ν = 3458, 2896, 1603, 1446, 1413, 1388, 1279,
˜
˜
1067 cm–1
.
1128 cm–1
.
2-[(4-Chlorophenyl)sulfonyl]-1-(4-fluorophenyl)ethan-1-ol (8c): Methyl
The representative experimental procedure was applied to S-(4- (13c): The representative experimental procedure was applied to S-
chlorophenyl) 4-chlorobenzenesulfonothioate (79.8 mg, 0.25 mmol) phenyl benzenesulfonothioate (62.6 mg, 0.25 mmol) with methyl
2-hydroxy-2-methyl-3-(phenylsulfonyl)propanoate
with 4-fluorostyrene (61 mg, 0.50 mmol) to afford 8c as white solid
methacrylate (75.1 mg, 0.75 mmol) to afford 13c as white solid in
in 90 % yield. M.p.: 124–126 °C. 1H NMR (CDCl3, 600 MHz): δ = 7.88–
65 % (41.6 mg) yield. M.p.: 67–69 °C. 1H NMR (CDCl3, 600 MHz): δ =
7.89 (m, 2 H), 7.55–7.57 (m, 2 H), 7.26–7.29 (m, 2 H), 7.01 (td, J = 7.90 (d, J = 7.6 Hz, 2 H), 7.65 (t, J = 6.9 Hz, 1 H), 7.56 (t, J = 7.6 Hz,
7.6, 2.1 Hz, 2 H), 5.28 (d, J = 9.6 Hz, 1 H), 3.57 (s, 1 H), 3.49 (dd, J =
2 H), 3.79 (s, 3 H), 3.77 (d, J = 4.8 Hz, 1 H), 3.75 (s, 1 H), 3.56 (d, J =
14.5, 10.3 Hz, 1 H), 3.31 (dd, J = 14.5, 1.4 Hz, 1 H) ppm. 13C NMR
14.5 Hz, 1 H), 1.46 (s, 3 H) ppm. 13C NMR (CDCl3, 150 MHz): δ =
(CDCl3, 150 MHz): δ = 162.7 (d, J = 245.6 Hz), 141.2, 137.8, 136.5 (d, 174.5, 140.7, 133.9, 129.3, 128.2, 72.5, 64.0, 53.5, 27.3 ppm. HRMS
J = 2.9 Hz), 129.9, 129.7, 127.6 (d, J = 7.1 Hz), 115.9 (d, J = 21.5 Hz),
(FAB, m/z): calcd. for C11H14O5S [M + 1]+, 259.0640; found 259.0643.
68.1, 64.1 ppm. HRMS (EI, m/z): calcd. for C14H12ClFO3S [M]+,
FTIR (neat): ν = 3504, 2955, 1746, 1580, 1445, 1426, 1378, 1304,
˜
314.0180; found 314.0182. FTIR (neat): ν = 3457, 2928, 1603, 1508,
1250, 1135 cm–1
.
˜
1302, 1132, 1087 cm–1
.
Benzyl 2-hydroxy-2-methyl-3-(phenylsulfonyl)propanoate (14c):
1-(4-Chlorophenyl)-2-tosylethan-1-ol (9c): The representative ex- The representative experimental procedure was applied to S-phenyl
perimental procedure was applied to S-(p-tolyl) 4-methylbenzene- benzenesulfonothioate (62.6 mg, 0.25 mmol) with benzyl meth-
sulfonothioate (69.6 mg, 0.25 mmol) with 4-chlorostyrene (69 mg, acrylate (88.1 mg, 0.50 mmol) to afford 14c as yellow solid in 65 %
1
0.50 mmol) to afford 9c as white solid in 60 % (46.6 mg) yield. M.p.:
(54.2 mg) yield. M.p.: 65–66 °C. H NMR (CDCl3, 600 MHz): δ = 7.86
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(d, J = 7.6 Hz, 2 H), 7.62 (t, J = 7.6 Hz, 1 H), 7.52 (t, J = 7.9 Hz, 2 H),
7.35–7.39 (m, 5 H), 5.26 (d, J = 12.4 Hz, 1 H), 5.14 (d, J = 11.7 Hz, 1
H), 3.80 (s, 1 H), 3.76 (d, J = 14.5 Hz, 1 H), 3.56 (d, J = 15.1 Hz, 1 H),
1.45 (s, 3 H) ppm. 13C NMR (CDCl3, 150 MHz): δ = 173.9, 140.8, 134.9,
133.8, 129.2, 128.7, 128.6, 128.1, 72.5, 68.5, 63.9, 27.2 ppm. HRMS
(FAB, m/z): calcd. for C17H18O5S [M + 1]+, 335.0953; found 335.0950.
with styrene oxide (90.1 mg, 0.75 mmol) to afford 4e as white solid
in 87 % (60.4 mg) yield. M.p.: 139–140 °C. 1H NMR (CDCl3, 600 MHz):
δ = 7.38–7.39 (m, 2 H), 7.30–7.32 (m, 1 H), 7.23–7.26 (m, 2 H), 7.19
(d, J = 8.3 Hz, 2 H), 7.03–7.05 (m, 2 H), 4.58–4.62 (m, 1 H), 4.33 (q,
J = 4.4 Hz, 1 H), 4.07–4.11 (m, 1 H), 2.98 (q, J = 4.6 Hz, 1 H), 2.40 (s,
3 H) ppm. 13C NMR (CDCl3, 150 MHz): δ = 145.2, 133.9, 131.2, 129.7,
FTIR (neat): ν = 3473, 2984, 1739, 1585, 1456, 1446, 1383, 1307, 129.6, 129.2, 128.8, 72.9, 61.5, 21.8 ppm. HRMS (EI, m/z): calcd. for
˜
1187, 1142 cm–1
.
C15H16O3S [M]+, 276.0820; found 276.0823. FTIR (neat): ν = 3529,
˜
2929, 1593, 1454, 1284, 1135, 1082 cm–1
.
Allyl 2-hydroxy-2-methyl-3-(phenylsulfonyl)propanoate (15c):
The representative experimental procedure was applied to S-phenyl
benzenesulfonothioate (62.6 mg, 0.25 mmol) with allyl methacrylate
(94.6 mg, 0.75 mmol) to afford 15c as yellow oil in 60 % (42.4 mg)
yield. 1H NMR (CDCl3, 600 MHz): δ = 7.89–7.91 (m, 2 H), 7.65 (td, J =
7.9, 1.6 Hz, 1 H), 7.54–7.57 (m, 2 H), 5.92–5.99 (m, 1 H), 5.37 (dt, J =
17.2, 1.4 Hz, 1 H), 5.30 (dt, J = 10.3, 1.4 Hz, 1 H), 4.71–4.75 (m, 1 H),
4.60–4.63 (m, 1 H), 3.78 (d, J = 14.5 Hz, 1 H), 3.75 (s, 1 H), 3.57 (d,
J = 14.5 Hz, 1 H), 1.47 (s, 3 H) ppm. 13C NMR (CDCl3, 150 MHz): δ =
173.8, 140.8, 133.9, 131.4, 129.3, 128.2, 119.5, 72.5, 67.3, 63.9, 27.4
ppm. HRMS (FAB, m/z): calcd. for C13H16O5S [M + 1]+, 285.0797;
2-[(4-Methoxyphenyl)sulfonyl]-2-phenylethan-1-ol (5e): The rep-
resentative experimental procedure with temperature modifica-
tion(100 °C) was applied to S-(4-methoxyphenyl) 4-methoxy-
benzenesulfonothioate (77.6 mg, 0.25 mmol) with styrene oxide
(90.1 mg, 0.75 mmol) to afford 5e as white solid in 71 % (51.6 mg)
yield. M.p.: 85–86 °C. 1H NMR (CDCl3, 600 MHz): δ = 7.42 (dd, J =
6.9, 2.1 Hz, 2 H), 7.30–7.33 (m, 1 H), 7.24–7.26 (m, 2 H), 7.04 (d, J =
6.9 Hz, 2 H), 6.85 (dd, J = 6.9, 2.1 Hz, 2 H), 4.60 (d, J = 8.3 Hz, 1 H),
4.32 (q, J = 4.4 Hz, 1 H), 4.07–4.10 (m, 1 H), 3.85 (s, 3 H), 3.00 (q, J =
4.6 Hz, 1 H) ppm. 13C NMR (CDCl3, 150 MHz): δ = 164.1, 131.4, 131.4,
129.7, 129.2, 128.8, 128.3, 114.1, 73.0, 61.6, 55.8 ppm. HRMS (EI,
m/z): calcd. for C15H16O4S [M]+, 292.0769; found 292.0766.
found 285.0793. FTIR (neat): ν = 3478, 3062, 2932, 1738, 1650, 1585,
˜
1447, 1383, 1308, 1191, 1142 cm–1
.
FTIR (neat): ν = 3527, 2931, 1594, 1498, 1281, 1263, 1132, 1083,
˜
1026 cm–1
.
2-Phenyl-2-(phenylsulfonyl)ethan-1-ol (1e): The representative
experimental procedure was applied to S-phenyl benzenesulfono-
thioate (62.6 mg, 0.25 mmol) with styrene oxide (60.1 mg,
0.50 mmol) to afford 1e as yellow solid in 86 % (56.4 mg) yield.
2-(4-Bromophenyl)-2-(phenylsulfonyl)ethan-1-ol (6e): The repre-
sentative experimental procedure was applied to S-phenyl
benzenesulfonothioate (62.6 mg, 0.25 mmol) with 2-(4-bromo-
phenyl)oxirane (99.5 mg, 0.50 mmol) to afford 6e as white solid in
50 % (42.7 mg) yield. M.p.: 127–128 °C. 1H NMR (CDCl3, 600 MHz):
δ = 7.60–7.62 (m, 1 H), 7.55 (dd, J = 8.3, 1.4 Hz, 2 H), 7.44 (t, J =
7.9 Hz, 2 H), 7.37–7.39 (m, 2 H), 6.94 (d, J = 8.3 Hz, 2 H), 4.56 (dd,
J = 12.4, 7.6 Hz, 1 H), 4.31 (q, J = 4.1 Hz, 1 H), 4.09 (dd, J = 11.7,
4.1 Hz, 1 H), 2.96 (s, 1 H) ppm. 13C NMR (CDCl3, 150 MHz): δ = 136.8,
134.3, 132.0, 131.3, 130.1, 129.1, 129.1, 123.7, 72.1, 61.2 ppm. HRMS
(EI, m/z): calcd. for C14H13BrO3S [M]+, 339.9769; found 339.9765. FTIR
1
M.p.: 158–159 °C. H NMR (CDCl3, 600 MHz): δ = 7.57–7.60 (m, 1 H),
7.51–7.53 (m, 2 H), 7.41 (t, J = 7.9 Hz, 2 H), 7.30–7.32 (m, 1 H), 7.24
(q, J = 7.1 Hz, 2 H), 7.03–7.04 (m, 2 H), 4.63 (dd, J = 12.4, 8.3 Hz, 1
H), 4.36 (q, J = 4.1 Hz, 1 H), 4.12 (d, J = 12.4 Hz, 1 H), 2.93 (s, 1 H)
ppm. 13C NMR (CDCl3, 150 MHz): δ = 136.9, 134.1, 131.0, 129.7,
129.3, 129.2, 128.9, 128.8, 72.9, 61.4 ppm. HRMS (FAB, m/z): calcd.
for C14H14O3S [M + 1]+, 263.0742; found 263.0740. FTIR (neat): ν =
˜
3506, 2918, 1582, 1444, 1295, 1142, 1056 cm–1
.
(neat): ν = 3500, 2922, 1591, 1489, 1303, 1144, 1064 cm–1
.
2-[(4-Fluorophenyl)sulfonyl]-2-phenylethan-1-ol (2e): The repre-
sentative experimental procedure was applied to S-(4-fluorophenyl)
4-fluorobenzenesulfonothioate (71.6 mg, 0.25 mmol) with styrene
oxide (60.1 mg, 0.50 mmol) to afford 2e as white solid in 70 %
(48.4 mg) yield. M.p.: 117–118 °C. 1H NMR (CDCl3, 600 MHz): δ =
7.51 (tt, J = 7.5, 2.2 Hz, 2 H), 7.31–7.34 (m, 1 H), 7.25–7.27 (m, 2 H),
7.04–7.09 (m, 4 H), 4.63 (t, J = 10.3 Hz, 1 H), 4.34 (q, J = 4.4 Hz, 1
H), 4.11–4.15 (m, 1 H), 2.89 (s, 1 H) ppm. 13C NMR (CDCl3, 150 MHz):
δ = 166.1 (d, J = 255.8 Hz), 133.0, 132.1 (d, J = 10.1 Hz), 131.0, 129.7,
129.5, 128.9, 116.3 (d, J = 23.1 Hz), 73.1, 61.4 ppm. HRMS (FAB, m/z):
calcd. for C14H13FO3S [M + 1]+, 281.0648; found 281.0649. FTIR
˜
2-(4-Bromophenyl)-2-(phenylsulfonyl)ethan-1-ol (7e): The repre-
sentative experimental procedure with temperature modifica-
tion(100 °C) was applied to S-phenyl benzenesulfonothioate
(62.6 mg, 0.25 mmol) with 2-(p-tolyl)oxirane (100.6 mg, 0.75 mmol)
to afford 7e as white solid in 73 % (50.2 mg) yield. M.p.: 114–115 °C.
1H NMR (CDCl3, 600 MHz): δ = 7.59 (t, J = 7.6 Hz, 1 H), 7.54 (d, J =
7.6 Hz, 2 H), 7.41 (t, J = 7.9 Hz, 2 H), 7.05 (d, J = 8.3 Hz, 2 H), 6.92
(d, J = 8.3 Hz, 2 H), 4.59 (s, 1 H), 4.32 (q, J = 4.4 Hz, 1 H), 4.08 (d,
J = 4.1 Hz, 1 H), 2.92 (t, J = 4.5 Hz, 1 H), 2.31 (s, 3 H) ppm. 13C NMR
(CDCl3, 150 MHz): δ = 139.3, 137.0, 134.0, 129.6, 129.5, 129.2, 128.9,
127.9, 72.6, 61.5, 21.3 ppm. HRMS (EI, m/z): calcd. for C15H16O3S
(neat): ν = 3519, 2930, 1587, 1492, 1288, 1140, 1063 cm–1
.
˜
[M]+, 276.0820; found 276.0816. FTIR (neat): ν = 3465, 2925, 1582,
2-[(4-Chlorophenyl)sulfonyl]-2-phenylethan-1-ol (3e): The repre-
sentative experimental procedure with temperature modifica-
tion(100 °C) was applied to S-(4-chlorophenyl) 4-chlorobenzene-
sulfonothioate (79.8 mg, 0.25 mmol) with styrene oxide (60.1 mg,
0.50 mmol) to afford 3e as white solid in 70 % (52.1 mg) yield. M.p.:
˜
1445, 1275, 1135, 1061 cm–1
.
1-(Phenylsulfonyl)hexan-2-ol (8e): The representative experimen-
tal procedure with temperature modification(100 °C) was applied
to S-phenyl benzenesulfonothioate (62.6 mg, 0.25 mmol) with 1,2-
epoxyhexane (75.1 mg, 0.75 mmol) to afford 8e as colorless oil in
1
97–98 °C. H NMR (CDCl3, 600 MHz): δ = 7.43 (dt, J = 9.0, 2.1 Hz, 2
1
H), 7.36 (dt, J = 9.0, 2.1 Hz, 2 H), 7.31–7.34 (m, 1 H), 7.26 (t, J =
7.6 Hz, 2 H), 7.06 (d, J = 6.9 Hz, 2 H), 4.62 (dd, J = 12.4, 8.3 Hz, 1 H),
4.35 (q, J = 4.4 Hz, 1 H), 4.13 (d, J = 12.4 Hz, 1 H), 2.91 (s, 1 H) ppm.
13C NMR (CDCl3, 150 MHz): δ = 140.9, 135.5, 130.8, 130.6, 129.7,
129.5, 129.3, 128.9, 73.0, 61.3 ppm. HRMS (FAB, m/z): calcd. for
78 % (47.3 mg) yield. H NMR (CDCl3, 600 MHz): δ = 7.93–7.95 (m,
2 H), 7.69 (t, J = 7.2 Hz, 1 H), 7.58–7.61 (m, 2 H), 4.14–4.18 (m, 1 H),
3.34 (d, J = 2.8 Hz, 1 H), 3.17–3.25 (m, 2 H), 1.53–1.56 (m, 1 H), 1.42–
1.46 (m, 1 H), 1.36 (tt, J = 7.5, 2.9 Hz, 1 H), 1.26–1.31 (m, 3 H), 0.87
(t, J = 7.2 Hz, 3 H) ppm. 13C NMR (CDCl3, 150 MHz): δ = 139.5, 134.1,
129.6, 128.0, 66.1, 62.4, 36.3, 27.2, 22.5, 14.0 ppm. HRMS (FAB, m/z):
calcd. for C12H18O3S [M + 1]+, 243.1055; found 243.1054. FTIR (neat):
C14H13ClO3S [M + 1]+, 297.0352; found 297.0355. FTIR (neat): ν =
˜
3472, 2927, 1577, 1475, 1315, 1145, 1083 cm–1
.
ν = 3521, 2932, 1590, 1447, 1304, 1142, 1084 cm–1
.
˜
2-Phenyl-2-tosylethan-1-ol (4e): The representative experimental
procedure with temperature modification(100 °C) was applied to 1-Phenoxy-3-(phenylsulfonyl)propan-2-ol (9e): The representa-
S-(p-tolyl) 4-methylbenzenesulfonothioate (69.6 mg, 0.25 mmol) tive experimental procedure with temperature modification(100 °C)
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0.25 mmol) with 1,2-epoxy-3-phenoxypropane (112.6 mg,
1
0.75 mmol) to afford 9e as colorless oil in 71 % (51.7 mg) yield. H
NMR (CDCl3, 600 MHz): δ = 7.97 (d, J = 6.9 Hz, 2 H), 7.68 (t, J =
7.6 Hz, 1 H), 7.59 (t, J = 7.9 Hz, 2 H), 7.26 (t, J = 8.3 Hz, 2 H), 6.96 (t,
J = 7.2 Hz, 1 H), 6.84 (d, J = 8.3 Hz, 2 H), 4.53 (d, J = 4.8 Hz, 1 H),
4.01 (qd, J = 9.9, 5.0 Hz, 2 H), 3.42–3.50 (m, 2 H), 3.38 (s, 1 H) ppm.
13C NMR (CDCl3, 150 MHz): δ = 158.1, 139.4, 134.2, 129.7, 129.6,
128.1, 121.7, 114.7, 70.1, 65.3, 59.6 ppm. HRMS (EI, m/z): calcd. for
C15H16O4S [M]+, 292.0769; found 292.0771. FTIR (neat): ν = 3482,
˜
2919, 1596, 1448, 1283, 1135, 1085 cm–1
.
Acknowledgments
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This study was supported by the C1 refinery program
(2015M3D3A1A01065436), the National Research Foundation of
Korea (No. 2016R1D1A1A09917100), and the Ministry of Trade,
Industry & Energy, Republic of Korea through the Human Re-
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of the Korea Institute of Energy Technology Evaluation and
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Keywords: Sulfonylation · Radical reactions · Sulfones ·
Reaction mechanisms · Synthesis design
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Received: May 21, 2018
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